Oil compositions



etented S p 194 2,408,102 on. so OSI'llllONS Herschel G. Smith, Wallingiord, and Troy L. Cantrell, Lansdowne, Pa", and John G. Peters, Audubon, N. 3., asslgnors to Gulf Oil Corporation, Pittsburgh, Pa", a corporation oi Pennsylvania No Drawing. Application Serial No. 583,658 8 Claims. (Cl. 252-35) of agents, capable of imparting a plurality of use-' ful, advantageous properties thereto; these improved oll compositions being useful and advantageous in protecting metals, both ferrous and non-ferrous metals, from rust, corrosion and wear. It also includes methods .of making such agents and improved oil compositions containing the same.

As is well known, the simple straight mineral oils usually are deficient in one or more respects, for certain commercial uses and it is common practice to incorporate one or more "additive compounds in the oil to overcome the defect or defects thereof for certain uses. Likewise, various agents have been incorported in oils to improve certain of their properties for particular or special uses requiring a superior oil. In general, such agents or additive compounds are known as improvement agents.

We have now discovered certain new improvement agents for mineral oils which are particularly advantageous in the commercial preparation of various lubricants, protective coating compositions and other useful mineral oil compositions. Our new agents can be readily incorporated in various mineral oils and oil compositions. When incorporated therein, even in very small amounts, these agents markedly improve the rust preventive qualities thereof. Further, they are also capable of imparting other useful and advantageous properties to mineral oils and oil compositions, as more fully described post.

Our. new and advantageous improvement agents for mineral oils and oil compositions are oil-soluble metal salts having the following formula:

wherein M is a trivalent metal, such as aluminum, etc., R is an alkyl group, and R represents an alhlol group. Thus, our improvement agents are substantially neutral trivalent metal salts of ortho phthalamidic acids, containing two alkyl groups attached tow the nitrogen atom thereof, one being a hydroxylated alkyl group, and the other a long chain alkyl group, as shown by the above formula.

as a class, the above metal salts are excellent improvement agents for mineral oils and oil composltionsand can be easily incorporated in such oil compositions, in proportions necessary for present purposes. All of these improvement agents are readily and markedly soluble in mining viscous liquids at elevated temperatures be-' low their decomposition point. Thus, in general, our improvement agents can be readily fluxed or blended with a wide variety of mineral oils and oil compositions and when incorporated therein improve various properties thereof;

On the other hand, our new improvement agents are water-resistant compounds which are practically insoluble in water and aqueous solutions. That is, they have a combination of properties which render them particularly advanta geous for the purposes of this invention, as is shown more fully post.

Further, these improvement agents can be readily prepared by various methods, as described in our companion copending application, Serial No. 608,100, filed July 31, 1945, wherein we claim these new oil-soluble metal salts and methods of making the same. As there described, our new improvement agents can be readily prepared, advantageou'sly in situ in mineral oil, directly from trivalent metal hydroxides, phthalic anhydride and secondary aliphatic amines having the followinggeously a long chain group containing from 8 to 2G carbon atoms, and R," represents hydrogen or an alkyl group, advantageously a short alkly group such as methyl, ethyl, propyl, butyl and the like;

In turn, these secondary alkyl amines containing a hydroml group attached to one of the alkyl 3 groups thereof can be readily prepared by reacting alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and the like with primary alkyl amines having the following tormula:

wherein n is a number between'6 and 18. Some of the primary alkyl amines of this generic class are Mono-capryl amine Mono-lauryl amine Mono-myristyl amine Mono-palmityl amine Mono-stearyl amine and other primary alkyl amines having the above formula. Any of the above primary iatty amines may be used witnadvantage in making the secondary amines useful for the present purposes, as all of them readily react with propylene oxide and similar alkylene oxides, as shown in our said comof sumcient mineral oil to dissolve the oil-soluble compound so obtained; the new improvement agents being formed in situ in the oil, as described and illustrated in our said companion-application Serial No. 608,100, g

Indeed in the practice of the present invention we usually prepare the desired trivalent metal salts in situ in mineral oil. The concentrated solutions of neutral trivalent metal salts in oil have certain advantages for the present purposes; they being themselves excellent improvement agents for imparting rust preventive qualities and other advantageous properties to a wide range of commercial compositions, such as greases, waxes, petrolatum and petrolatum-like coating compositions, as well as mineral oils and oil compositions.

The following examples illustrate various methods of preparing our improvement agents and lmprovedcompositions containing the same.

Example i'.-In this example, a substantially neutral aluminum salt was prepared, in situ in mineral oil, directly from phthalic anhydride, dodecyl prcpanol amine and a commercial hydrated alumina, said hydrated alumina being a gelatinous, aqueous paste containing 18 per cent aluminum hydroxide; the oil-soluble salt so prepared being a neutral aluminum salt of N-doinstance, one commercially available mixture of v such primary fatty amine is the socalled "cocoamine." As stated in'the said copending application, commercial cocoamine has an average molecular weight of 210 and contains a major amount of lauryl amine admixed with minor amounts of homologues thereof. This commercial fatty amine maybe employed with advantage in preparing secondary aliphatic amines useful in making our improved oil-soluble trivalent metal tions of propylene oxid and a long chain primary aliphatic amine are claimed in our copending application, Serial No. 640,128, filed January 9, 1946, as a continuation-in-part of the present application.

Further, as shown in our said copending application, in so preparing our agents from such secondary amines, phthalic anhydride and trivalent metal hydroxide, those chemicals are reacted together and converted into new compounds; they being chemically combined together in the molecular ratios necessary to produce our new substantially neutral oil-soluble trivalent metal salts having substantially the generic structure given ante. In doing so, we usually react said secondary amine with phthallo anhydride in substantially equimolecular amounts. to form a mono-amide of phthalic acid, namely, the desired N-alkyl, alkylol ortho phthalamidic acid, and then neutralize the residual acidity of that compound by reaction with hydrated alumina, sufficient aluminum hydroxide being employed to form substantially neutral aluminum salts thereof. In lieu of'hydrated alumina or aluminum hydroxide, other hydroxides and oxides of trivalent metals, such as bisdecyl, propanol ortho phthalamldlc acid and having the following formula:

The procedure in preparing this improvement agent was asfollows:

To 2390 grams of 70 viscosity Texas oil were added 444 grams of phthalie anhydride and the mixture vigorously stirred to disperse the phthalic anhydride ln-the oil. 'I'hen,'while continuing the stirring, 804 grams of n-dodecyl, isopropanol amine were gradually added to the oil mixture, the temperature of the mixture being maintained at approximately F. during the addition of the amine. After all the amine was added, the reaction mixture was heated to between 150 and F. until the reaction was substantially completed; that is, until the-amine-had reacted with the phthalic anhydride and converted it into the corresponding ortho phthalamidic acid. I

The oil solution of the N-alkyl, alkylol phthalamidic acid so obtained was a semi-viscous liq-- uid; this phthalamidic acid being readily soluble in mineral oils and being easily converted into metal salts, advantageously neutral aluminum salts, as follows:

In doing so, 78 grams of aluminum hydroxide,

.in the form of aqueous, gelatinous paste, was

admixed with. the'olly solution of the phthalamidic acid obtained ante. This mixture was then heated and the temperature gradually raised to 240 F. over the, course of two hours. The

The filtrate so obtained is an excellent improvement agent for present purposes; it being a concentrated solution of the said neutral aluminum salt in the mineral oil. approximately 33 per cent by weight of said aluminum salt. Nevertheless, it was an oily, mobile liquid at room temperature. This clearly shows the high solubility of our, new trivalent metal salts in mineral oils.

That is, the foregoing example is typical and illustrative of certain embodiments of this invention. In other embodiments thereof, other. secondary alkyl, alkylol amines can also be employed in making our improvement agents, as stated ante. For instance, in'Example 1, other secondary amines such as dodecyl butanol amine, hexadecyl propanol amine and the like may be employed in lieu of dodecyl propanol amine. Further, mixtures of such secondary alkyl, alkylol amines may likewise be employed with advantage, as illustrated in the following examples:

Example II.-This example illustrates the preparation of a mixture of secondary amines which are useful in making our oil-soluble metal salts; this mixture of secondary alkyl, alkylol ally heated to approximately 35 C. under reflux,

the heating under reflux being continued for about 15 hours to complete the reaction.

The reaction product so obtained was a, homogeneous, clear, semi-viscous liquid comprising a mixture of secondary fatty propanol amines containing a major amount of lauryl propanol amine. This mixture of secondary amines is useful and advantageous in preparing a wide variety of our new oil-soluble improvement agents. It readily reacts with phthalic anhydride to form N-allryl, alkylol ortho phthalamidic acids which in turn can be readily converted into various metal salts by reaction with trivalent metal hydroxides.

The preparation of one advantageous improvement agent from this mixture of secondary fatty propanol amines is illustrated in the following example:

Example III .-In this example, a. substantially neutral aluminum salt was prepared, in situ in a light mineral lubricating oil, directly from phthalic anhydride and commercial hydrated alumina, and the mixture of secondary amines obtained in Example II ante; the mineral oil being a 70 vis- I cosity Texas oil having the following properties:

Gravity: A. P. I 25.8 Viscosity, SUV:

It contained.

and the mixture was vigorously stirred to disperse the phthalic anhydride in theoil. Then, 804 pounds of the secondary fatty propanol amines obtained in Example II were gradually added to the oil mixture while continuing the stirring; the amines being gradually added and the temperature being maintained at approximately F. during this time. After all the amines were added, the reaction mixture was heated to between 150 and F. until the reactions were substantially complete. Next, 436 pounds of a commercial, gelatinous paste of hydrated alumina, containing 18 per cent of aluminum hydroxide, were gradually admixed with an oil solution of N-alkyl, alkylol phthalamidic acids obtained ante. After thoroughly incorporating the hydrated alumina paste in this mixture, the mixture was then heated to 240 F.; the temperature being gradually raised to quietly boil off the free water. Then the mixture was held at 240 to 250 F. to complete the reaction and fully dehydrate the oil solution of neutral aluminum salts so obtained.

The oil solution of anhydrous aluminum salts so obtained was then filtered while hot to remove any insoluble matter.

The flltrate so obtained is an excellent improvement agent for the present purposes. oily mobile liquid at room temperature and had the following properties:

It was a concentrated solution of substantially neutral aluminum salts of the ortho phthalamidic acids derived from said secondary amines. This oil solution contained approximately 33 per cent by weight of said aluminum salts. Nevertheless, it was an oily mobile liquid at room temperature. This clearly shows the high solubility of such salts in mineral oils.

This improvement agent had a good color and was substantially free of insoluble matter. It was readily miscible with various mineral oils and oil compositions and was directly soluble in most mineral oils in a manner effective for the present purposes. In particular, this improvement agent is useful and advantageous as an additive compound in preparing improved motor oils and like lubricants. It is also advantageous in preparing other improved oil compositions useful in protecting metals against abrasion and corrosion.

That is, the foregoing Examples I and III, respectively, are typical and illustrative of our new improvement agents and methods of making the same which are advantageous in certain embodiments of this invention. In other embodiments thereof, we may also employ various other trivalent metal hydroxides and secondary amines containing an alkylol group in making our improvement agents, as stated ante. For instance, the hydroxides of bismuth and other trivalent metals may. be used in Examples I and Ill ante, in lieu of aluminum hydroxide, to produce still other advantageous improvement agents.

In fact, by the present invention a wide range of improvement agents can be readily prepared in the generic practice thereof. All of them are readily soluble in commercial mineral oils and oil compositions in the proportions required to effect It was an positions for metals.

the desired improvements. Indeed, a wide range of improved anti-rust lubricants can be readily prepared by incorporating minor amounts of our improvement agents in suitable oils and oil compositions. In general, such improved anti-rust Further, the concentrated solutions of the .aluminum salts in oil, obtained in Examples I and III, are directly useful as rust preventive coating compositions for metals. They are substantially I non-corrosive to both ferrous and non-ferrous metals. When applied to such metals, they tightly adhere to the metal forming a protective coating thereon which is resistant to water and aqueous liquids and fully protects the metal against rust or corrosion, even when exposedto the most drastic conditions. That is, our new oil-soluble metal salts are very potent rust preventive compounds. Accordingly, they carnalso be compounded with various other materials in preparing a wide range of protective coating com- In particular, they are readily soluble in various hydrocarbon oils, particularly mineral lubricating oils. Further, they are also readily miscible with waxes, petrolatum and greases, as well as oil compositions.

Thus, our new improvement agents, such as obtained in Examples I and 111, are useful in preparing a wide range-of compositions having exceptional rust preventive properties; they being particularly advantageous in preparing improved anti-rust lubricants to which they impart further advantageous properties as shown post.

. no protection against rust.

Improved on Base oil Gravity: A. l'. I 32.4 32. B Viscosity SUV:

100 i 149 150 210 43.2 43.0 Neutralization No 0.01 0. 01

As shown by the above tabulation of properties, the incorporation of this improvement agentin the base 011 did not substantially change the physical properties thereof.

However, the improved' oil so obtained had markedly improved rust-preventive qualities. For instance, when subjected to various standard corrosion tests, it completely inhibited rusting of the metal, whereas the base oil gave little or In one such set of comparative tests the following data were obtained:

I Corrosion test, ASTM 1) 666-42 '1" g 'Base oil Distilled water-steel strip Bright Rusted 0 100 Synthetic sea water-steel strip:

, Appearance Bright Rusted Area rusted, percent 0 100 The said corrosion tests employed were standard tests for determining the rustpreventive properties of commercial. mineral oils and oil compositions.

As shown by the test data ante, our improved anti-rust oil had outstanding rust-preventive properties and satisfactorily passed said tests,

' ties and other advantageous properties shown Such improved lubricants can be readily obtained by incorporating small amounts of ourimprovement agents-in mineral lubricating oils, greases, petrolatum and the like. For instance, the improvement agents obtained in Examples I and III are readily "soluble in commercial mineral lubricating oils and when dissolved therein, even in small quantities, markedly improve various properties of such oil. For example, the mineral lubricating oils containing from 0.1 to 1.0 per cent by weight of such improvementagents have increased resistance to oxidation and deterioration, as well as improved rust preventing or corrosion preventing properties. v

The following example illustrates the preparation ofsuch improved lubricants and methods of making the same:

Example IV.In this example, one such ad vantageous anti-rust lubricant containing 0.1 per cent of the substantially neutral aluminum salts obtained in Example III ante, dissolved in a commercial mineral lubricating oil was prepared as parts by weight of the filtrate obtained in Example I were added to the oil with stirring. Stirring was continued until the improvement agent was uniformly and homogeneously blended with the oil. The properties of the improved oil and the base oil employed in making the same were as follows:

ante, our improvement agents are useful and advantageous in-a wide range of commercial oil .compositions. They may also be incorporated in minor amounts in other types of oils, such as turbine oils, instrument oils, electric motor oils and other high quality lubricants where it is important to protect metal surfaces from rust and corrosion, as well as adequate lubrication thereof under service conditions.

For example, improved turbine oils can be readily prepared by dissolving 0.03 to 3.0 per cent of our improvementagents, such as obtained in Examples I and III, in any of the commercial turbine oils. The preparation of one such improved turbine oil is illustrated in the following example: I

Example V.--In this example, an improved turbineoil was prepared by dissolving 0.15 per cent of the filtrate obtained in Example III in a suitable well-refined mineral lubricating oil. The improved lubricating oil contained 0.05 per cent of the substantially neutral aluminum salts of the phthalamidic acids obtained in Example III.

The properties of this improved lubricant and the base oil employed in making the same were as follows:

The above improved turbine oil, with this markedly low dosage of our highly efiective corrosion preventive agent, and without the addition of any supplemental corrosion preventive agent, successfully passed without any traces of rusting, the above described steel strip corrosion test.

In general, our improvement agents have proven to be quite satisfactory addition agents for turbine oils; particularly for compounded turbine oils of higher viscosity types, such as are preferred for marine service.

In other words, the plurality of advantageous properties can be imparted to turbine oils by incorporating our new improvement agents therein. Likewise, similar improvements can be obtained in other types of lubricants by incorporating our new agents in various oils and oil compositions.

For example, our new agents are also useful and advantageous in preparing improved motor oils for lubricating automotive, aviation and Diesel engines. Such improved oils can be readily prepared by incorporating a few per cent. of these improvement agents in a suitable mineral lubricating oil; usually 0.3 to 3.0 per cent by weight of the oil." The compounded oils so obtained have improved detergent properties as well as other advantageous properties. In general, such improved motor oils containing minor amounts of our agents have a plurality of advantageous properties. In addition to protecting metals from rust and corrosion, they have superior lubricating properties, even under severe operating conditions.

In particular, this invention relates to improved lubricating oils containing a multifunctional improvement agent having anti-oxidant and other advantageous properties such as high film fstrength. Moreover, the lubricating oils to which our inhibitor is added are capable of retarding the formation of all forms of gum, resins, carbon, and varnish-like materials which are usually formed on the pistons and rings of internal combustion engines. In addition to the property of being able to inhibit the formation of products capable of corroding sensitive metallic bearings normally found in internal combustion engines or other metals contacted with the oil, all oils containing our improvement agents and minor proportions of Water or salt water are inhibited against corrosion tendencies. That is, our improved lubricating compositions comprising a major amount of a petroleum lubricating oil and a minor amount of our new additive compounds have improved detergent, anthoxidant and other advantageous properties.

That is, our new improvement agents impart this invention relates to improved mineral oil compositions containing minor amount of substantially neutral trivalent metal salts of N-alkyl, alkylol ortho phthalamidic acids, as a new and advantageous improvement agent; the amount of such improvement agent being sufiicient to impart thereto the advantageous properties desired. In general, our improved oil compositions usually contain from 0.01 tov 10.0 per cent by weight of such improvement agents dissolved in the mineral oil.

This application is a continuation-in-part of our prior application Serial No. 566,402, filed December 2, 1944, which became U. S. Patent No. 2,378,443 on June 19, 1945, which also relates to improved oil compositions and methods of making the same.

In our said prior application, we have described and claimed improved 'mineral oil compositions containing a minor amount of oil-soluble aluminum phthalyl alkyl amide compounds having the following formula:

wherein R represents an alkyl group containing 8 to 20 carbon atoms. Such oil-soluble compounds can be readily produced from the reaction or inter-action of aluminum hydroxide, phthalic anhydride and primary alkyl amines, advantageously in situ in mineral oil, as described and illustrated in our prior application. As there shown, the improvement agents so obtained impart a plurality of valuable properties to mineral oils and oil compositions and are advantageous for such purposes.

The oil-soluble aluminum phthalyl alkyl amide compounds employed in our prior application are substantially neutral aluminumsalts of a monoto mineral oil compositions a plurality of advention a Wide range of improved mineral oil compositions can be readily prepared, including excellent protective coating compositions, as well as improved anti-rust lubricants. Thus, broadly,

alkyl amide of phthallc acid, as shown by the above generic formula. They are also designated as aluminum N-alkyl amido phthalates, as stated in our prior application. However, as is evident from the above formula, these oil-soluble salts are substantially neutral trivalent metal salts of ortho phthalarnidic acids containing a long chain alkyl group attached to the nitrogen thereof, which carries a reactive hydrogen attached thereto.

The oil-soluble salts employed in the present invention are substantially neutral trivalent metal salts of ortho phthalamidic acid containing an alkylol group attached to the nitrogen atom thereof, in addition to the long chain alkyl group attached thereto. new improvement agents are alkylol derivatives of the improvement agent set forth in our prior application. Indeed, they can be prepared by reacting said neutral aluminum phthalyl alkyl amides with propylene oxide and similar alkylene oxides; thereby substituting an alkylol group for the hydrogen attached to the nitrogen atom into the ortho phthalamidic salt shown in our prior Thus, so to speak, our' QLAWEQ mccnsrcnrn n nio-o-o'n no- -cm rherein M represents a trivalent metal. R" repesents hydrogen oran alkyl group, and n is a umber between 6 and 18. As a' class, these trialent metal salts are useful and advantageous l2 wherein M is a trivalent metal. R is an alkyl group and R is an alkylol group. and the amount of said metal salt being suflicient to impart corrosin-inhibiting properties to the improved oil or the present purposes. particularly the neural aluminum salts having the above formula.

That is, we have now found that by substituting n alkylol group :Ior the hydrogen attached to he nitrogen atom oi. the ortho phthalamidic acid alts shown in our prior application, Serial No. 66,402, now U. S. patent No. 2,378,443, we obtain new and diflerent class of improvement agents r polyvalent metal salts which in addition to aving greater solubility in mineral Oils also. have ther modified properties which render them paricularlyuseful as improvement agents for iineral oils and oil compositions; these improveients being in part due to the presence of the lkylol group in the molecule of our new improve- 1ent agents. The present application is broadly irected to improved mineral oil compositions ontaining these new improvement agents.

What we claim is: i 1. An improved mineral oil composition comrising a major amount of a mineral oil and a 11110! amount of an oil-soluble trivalent metal ilt of N-alkyl, alkylol ortho phthalamidic acid, rid metal salt having the following iormula composition. 2. The composition of claim 1 wherein the said mineral oil composition 'contains from 0.01 to 10.0 per cent by weight of said improvement agent dissolved in the mineral oil.

neutral aluminum salt of N-dodecyl propanol ortho phthalamidic acid.

5. The improved composition of claim 1 wherein the said oil-soluble metal salt is a substantially neutral aluminum salt of N-dodecylethanol orth phthalamidic acid.

6. The improved composition of claim 1 wherein the said oil-soluble metal salt is a substantially neutral aluminum salt of N-hexadecyl butanol 'ortho phthalamidic acid.

7. An improved mineral oil composition comprising a major amount of a mineral lubricating oil containing dissolved therein. from 0.01 to 10.0 per cent by weight oi! an oil-soluble, trivalent metal salt'ot N-alkyl, alkylol phthalamidic acid, said metal salt having the following formula:

I o o t 0 I I QE-o-Ilao-AQ nic-(cmn-cnriw H H N-CHr-(CHOn-CH; H: 443-015 HQ-- H:

II I! 

